Method of waterproofing textiles with zirconyl compounds



Petented Se t. 27, 1949 I I 2,482,816

UNITED STATES PATENT OFFICE METHOD OF WATERPROOFING TEXTILES WITHZIRCONYL COMPOUNDS Henry L. Van Mater, Highland Park, N. J., as-

signor, by mesne assignments, to National Lead Company, New York, N. Y.,a corporation of New Jersey No Drawing. Application June 8, 1943, SerialNo. 490,079

8 Claims- (Cl. 117-167) This invention relates to the employment of Sluti However, if this compound is treated certain salts of zirconium, aswater repellent w a hydrous methanol or ethanol, free stearlc orwaterproofing agents for textiles and to meth-' acid is extracted fromit in an amount correods for treating textiles with such salts. p g to eole of the free acid for ea h Heretofore it has been proposed to' employ5 mole f e al o pound. The remaining water insoluble soaps as waterrepellents for texalcohol insoluble esidue y analysis corresponds tiles.The term water repellent is, however, a o the fo ula O(OH)C11H35COO.

purely relative term and the materials presently Th Would ca e that theformula of the employed to rendertextiles water resistant leave orlglnalmpound Should have been much room for improvement.

. It is an object of the present invention to pro- ZICKOH)cnHucoo'cnHsscooH vide a composition and method rendering The alcoholinsoluble residue corresponds exactly textile goods w e resistant withthe compound formed it one mole of zirconyl In accordance with thepresent invention zirchloride is reacted with one mole of Sod-u coniumsalts are de t d 15 1 m posi e upon and employed t to impregnate textilegoods to render the same Example 2. If t one mole of precipitated Waterresistant; certain zlrcomum conyl carbonate there is added one mole ofacetic z po t i Which ether g fi g agi acid, the solution of thezirconyl carbonate is f P ures or er con 9 con quite incomplete. If,however, two moles or more acldlty are used and partlcula-rlv zlrcomumof acetic acid is added the solution is complete.

co p o e Water Soluble fatty aoids- Careful evaporation of this solutioncontaining The folloWmg 15 presented as one explanation two or moremoles of acetic acid yields an acetate of the reactions involved. Otherexplanations, corresponding t t formula may be possible.

ZrO(CH3COO) aHaO This compound is water soluble and perfectly stable inair at room temperature. If gently heated or placed in a vacuum, aceticacid is given Proof may be found in the literature that certain hydratedcompounds of zirconium sulfate which were formerly assigned a formulasuch as Zr(SO4) 2XH2O should in reality have the formulaZrOSO4.HzSO4.(X1)HzO. .This ability of ziroff in an amount corres ondmto on 1 conyl compounds to form co'ordmatlon mole of the original 0013113011115. The r sidiie pounds, in the above case, with a molecule ofwater Soluble 1 free sulfuric acid, is further supplemented by its i;ga? 1 5 ysls corresponds o ablhty to form double salts Such as A threeper cent solution of the basic zirconyl ZrOSO4.NazSO4.XI-IzOacetate-acetic acid compound etc.

Many references in the literature may be found I Zr0(OH) (CI-RG00) m Ywhich refer to basic zirconyl compounds but few shows no hydrglysis onStanding t room t a p to postulate a formula for Such 'perature forseveral weeks. A one percent solupoundshave been made. 40 tion of thissalt shows evidence of hydrolysis on My investigations give evidencethat aqueous t di for t t tw lv h solutions of certain salts ofzirconium produce Freshly prepared mm of thi lt h compounds in which thezirconium atom exists no evidence of hydrolysis up t 40 c, t 50 c,

in a basic zirc y d c of the m hydrolysis takes place rapidly asindicated by the ZrOOH+ formation of an insoluble compound. AnalysisExample 1.If one mole of a soluble c y of this insoluble compoundindicates that it also salt, for example ZrOC12.7H2O, is allowed toreact h the formula, Zr0(0H) (CH3COO),

with two moles of a soluble stearate, for example vAnother method ofproducing the same insol- CivHasCOONa, there is formed a water insolubleuble compound is to raise the pH of the solution compound,'the analysisof which corresponds to by the addition of an alkaline salt, which doesZIO(C17H35COO)2.H2O. v not form an insoluble compound with zirconium,

This compound is completely soluble in certo approximately pH 6. Thezirconium is then tain organic solvents such as benzene, toluene,precipitated as the basic zirconyl acetate,

etc., from which it may be recovered by evaporarO(OH) (CI-1 3000) andhas the same properties tion of the solvent or by cooling a hotsaturated as that produced by heating.

Apparently at temperatures above 50 C. or by the elevation of the pH ofthe solution the coordination linkage between the basic zirconyl acetateandthe acetic acid is broken and the acetic acid is replaced by watermolecules.

In this hydrated state the compound appears to hold two molecules ofwater- The loss in weight in air dried samples when dried at 105 C.corresponds to this amount.

While in this hydrated state this basic zirconyl acetate still showsstrong ability to form coordination compounds. Metallic salts which areacid in character and organic compounds which contain an acid group,particularly the sulfonic acid group, will add themselves to the basiczirconyl acetate.

Apparently an equilibrium is set up between the tendency of the watermolecules to hydrate the basic zirconyl acetate and the tendency of theacid compounds to co-ordinate with it. Such co-ordination reactions arenever complete and the attached molecules of acid character may beremoved by repeated washing.

However, if the co-ordination compounds formed bythe basic, zirconylacetate and the acidic type of molecules are filtered off and dehydratedcompletely then the attached acid type of molecule can no longer beremoved by washing.

Apparently sufficient shrinkage of the crystal lattice occurs in thedehydration so that the molecule will no longer become hydrated and theequilibrium condition re-established.

Like the zirconyl sulfate, referred to above, the hydrogen of the aceticacid molecule inthe compound ZrO(OH) (CH:COO).CH3COOH may be replaced bya metallic ion. conditions the double salt ZrO(OH) (CHaCOO).CHsCOONELXHzO may be formed.

Phenomena parallel to those observed with the reactions betweenzirconium carbonate and acetic acid and the formation and hydrolysis ofthe resulting salt, may likewise be observed with zirconium carbonateand formic acid or other organic acids.

The terms zirconyl coordination salt" or zirconyl coordination compoundrefer to molecular associations of a free acid and a normal zirconylsalt. The reactions and constitution of these molecular complexes appearto con form with the coordination theory of Werner (see A ComprehensiveTreatise on Inorganic and Theoretical Chemistry, by J. W. Mellor, vol.VIII, Longmans Green and Co., 1928, pages 228-242).

One of the outstanding characteristic properties of the basic zirconyl(ZrOOH compounds of acetic, formic and certain other organic acidstogether with the co-ordination compounds with aids or compounds of acidnature derived therefrom are their hydrophobic or water repellentnature.

Therefore, the purpose of this invention is to describe the method ofpreparing and applying such hydrophobic zirconium compounds to textilematerials in such a way-as to render the treated materials waterrepellent.

Example I.-The textile sample of cotton, rayon, wool, silk or othermaterial of vegetable or animal origin is treated by saturating theSample with adilute, for example, a one per cent Under proper solutionof the acetic acid co-ordination compound of basic zirconyl acetateZrO(OH) (CHiCOO) .CHaCOOH which may also be referred to as zirconylacetate monohydrate ZrO(CHaCOO) a.HnO for a period of thirty seconds atany convenient temperature up to approximately C. The textile materialis then removed from the bath and the excess solution removed bywringing or centrifuging. The

Example II.The textile sample of cotton,

rayon, wool, silk or other material of vegetable or animal origin, istreated in a dilute, for example a one per cent, solution of the aceticacid co-ordination compound of basic zirconyl mately thirty seconds.

acetate, mentioned in Example No. 1. The excess solution is removed andthe textile sample is then introduced into a dilute solution of borax orother alkaline salt containing a negative ion which does not form aninsoluble compound with zirconium. The alkalinity of the borax or othersolution raises the pH of the solutionand causes precipitation of thebasic zirconyl acetate ZrO(OH) (CHaCOO) within and on the surface of thefibres of the sample. The sample is then washed with warm water anddried at to C.

Example III.-The textile sample of cotton, rayon, wool, silk or othermaterial of vegetable or animal origin is treated in a dilute, forexample a one-percent, solution of the sodium acetate co-ordinationcompound of basic zirconyl acetate at any convenient temperature up to40 C. for approximately thirty seconds. The sample is then steamed,washed and dried as described above.

Example IV.The textile sample is first treated in a dilute, for examplea one per cent, solution of the sodium acetate co-ordination compound ofbasic zirconyl acetate at any convenient temperature up to 40 C. forapproxi- The sample is then treated in a bath containing a dilutesolution of borax or other basic salt mentioned above. The procedurethereafter is the same as in Example II.

Example V.--The textile sample is firsttreated with a dilute, forexample a one per cent, solution of the formic acid co-ordinationcompound of basic zirconyl formate The procedure thereafter is the sameas described in Example I.

Example VL-The textile sample is treated with a dilute, for example aone per cent, solution of the formic acid co-ordination compound ofbasic zirconyl formate at any convenient tem- Example VII.The textilesample consisting of cellulose, regenerated cellulose, rayon or othercellulosic material is treated with a solution of the acetic acidco-ordination compound of basic zirc nyl acetate, 'ZrO(OI-I)CHaCOOCHzCOOH, of convenient concentration, for example a solutioncontaining from four to seven per cent of the salt. The treatment iscarried out preferably at 40" C. or below for approximately thirtyseconds. Excess solution is removed from the sample and the sample isthen dried in moderately warm air.

Varying conditions of drying may be used, depending upon the temperatureof the air and its rate of flow over the sample. The drying should notbe carried out too rapidly since time is required to allow the aceticacid portion of the molecule to react with the cellulose.

Regenerated cellulose is particularly adaptable to treatment by thismethod.

Example VIII .The textile sample of cellulosic material is treated witha solution of the formic acid co-ordination compound of basic zirconylformate of convenient concentration at 40 C. or

' below for approximately thirty seconds. The subsequent procedure isthe same as in Example VII.

Example IX.--If sulfanilic acid is added to a solution containing abasic zirconyl salt of a water soluble fatty acid, for example theacetic acid co-ordination compound of basic zirconyl acetate referred toabove, so that the ratio of sulfanilic' acid and the basic zirconylcompound are mole for mole, the resulting stable solution may be usedfor the impregnation of textile fabrics to obtain water repellence.

The textile sample is immersed in such a solution having a content of,for example, 3.5% ZrOn. The excess solution is removed by wringing orcentrifuging and the sample is dried at 100 to 105 C. Excellent waterrepellent properties are obtained.

Example X.--Basic zirconyl stearate ZrOOHCnHasCOO also known aszirconium mono stearate, is soluble in certain organic solvents andforms colloidal suspensions with others.

This compound may be dissolved or suspended as a colloid in thesolutions used for dry cleaning purposes. The addition of from one totwo per cent of this compound to the last rinsing solution used in drycleaning operations not only renders the textile material waterrepellent, but also considerably increases its resistance to creasing.

Textile goods treated by the above methods gave excellent results whentested for water repellence, either by the hydrostatic or spray methods.Further, certain heavy cotton fabrics exhibited excellent weatherresistance over a period of several months as well as under standardaccelerative tests. Cotton duck, for instance, when treated inaccordance with the procedure of Example I showed resistance to ahydrostatic head of 18 inches which was reduced by 3 to 4 inches afterwashing for 15 minutes with percent of soap as against a reduction of 50per cent in instances where the material is treated in conventionalmanner.

What is claimed is:

1. The step in the method of rendering textile goods water repellentwhich comprises treating the goods with a solution of a water soluble 3.The method of rendei j ing textile goods water repellent which comprisestvettingthe goods with a solution containing a water soluble zirconylcoordination salt of an aliphatic acid at a temperature below thedecomposition temperature of said compound and thereafter heating the sowetted goods to a temperature above its decomposition temperaturewhereby said compound is changed to a water insoluble condition.

4. The method of rendering textile goods water repellent which compriseswetting the goods with a solution containing a water soluble zirconylcoordination salt of an. aliphatic acid at a temperature below about 40C. and thereafter heating the so wetted goods to a temperature aboveabout 40 C. until said compound has changed to a water insolublecondition.

5. The method of rendering textile goods water repellent'which compriseswetting the goods with a solution of a zirconyl coordination salt of awater soluble fatty acid and then heating the so wetted goods to atemperature above the decomposition temperature of said salt wherebysaid salt is changed to a water insoluble condition.

6. The method of rendering textile goods water repellent which compriseswetting the goods with a solution of a zirconyl coordination salt of awater soluble fatty acid and an organic acid and thereafter drying thegoods at a temperature above 40 C.

v 7. The method of rendering textile goods water repellent whichcomprises wetting the goods with a solution of a zirconyl coordinationsalt of a water soluble fatty acid and an organic acid and thereafterdrying the goods in the neighborhood of C.

8. The method of rendering textile goods water repellent .whichcomprises wetting the goods with a mole for mole solution of the aceticacid co-ordination compound of basic zirconyl acetate and sulfanilicacid and thereafter drying the goods in the neighborhood of 100 C.

HENRY L. VAN MATER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,536,254 White May 5, 19251,717,483 White June 18, 1929 1,739,840 Kendall Dec. 17, 1929 1,896,381Weber et al. -1.. Feb. 7, 1933 1,898,105 Weber et a1. Feb. 21, 19331,925,914 Tanker Sept. 5, 1933 2,221,975 Kinzie et a1. Nov. 19, 19402,316,057 Doser et a1. Apr. 6, 1943 2,316,141 /Wa iner Apr. 6, 19432,328,431 Doser et a1. Aug. 31, 1943 2,345,142 Muller Mar. 28, 1944FOREIGN PATENTS Number Country 1 Data 4,457 Great Britain Mar. 16, 1918

